Polymerizable phosphazene derivatives: a process for preparing them and their uses

ABSTRACT

This invention relates to a polymerizable phosphazene derivative with a general structural formula 
     
         .brket open-st.NP(A).sub.a (B).sub.b).brket close-st..sub.x 
    
     wherein the groups A and B are bonded to phosphorus atoms through --O--, --S--, --NH--, or --NR-- (with R=C 1  -C 6 ) alkyl), and wherein A stands more precisely for a vinyl ether group or a styrene ether group, and B stands more precisely for a hydrocarbon group. The invention also relates to procedures for synthesizing such phosphazene derivatives. The phosphazenes derivatives of the invention can be cured by a process that is initiated cationically, which leads to a large number of advantages. The phosphazene derivatives of the invention can, in particular, be used as curable binders for paints, coatings, fillers, mastics, adhesives, moldings, or films. Paints or coatings comprising the phosphazene derivatives of the invention show especially high mechanical resistance and scratch resistance.

This application is a division of application Ser. No. 08/840,839, filedApr. 17, 1997, now U.S. Pat. No. 5,912,321.

This application claims the priority of German patent document 196 16968.2-43, the disclosure of which is expressly incorporated by referenceherein.

BACKGROUND AND SUMMARY OF THE INVENTION

Patent document EP-A-0 557 943 describes phosphazene compounds that canbe cured by radical polymerization, the polymerization of which isinitiated by adding initiators or by electron radiation. Patent documentEP-A-0 368 165 describes curable resin compositions that contain acurable phosphazene compound and a pentaerythritol acrylate compoundand/or a bis(4-acryloxydialkoxpheyl)alkane compound mixed together.These known phosphazene derivatives have one or more of the followingdrawbacks. They tend to polymerize prematurely, so that stabilizers haveto be added. High storage temperatures have to be avoided, which in turnresults in drawbacks for shelf life and choice of conditions forsynthesis, yields, and absence of chlorine. Radical polymerization isinhibited by atmospheric oxygen and thermal curing in particularfrequently leads to incompletely hardened surfaces. Curing often occursvery slowly and leads to products that discolor with time. During thecuring, severe shrinkage frequently occurs that leads to deteriorationof behavior and cracking. So, such phosphazene derivatives, or theirmixtures pursuant to the state of the art, cannot be used for manyapplications, including use as binders for paints and coatings inparticular.

The invention makes available new phosphazene derivatives that avoidthese drawbacks of the state of the art and provides polymerizableproducts with improved properties. In particular, it is desirable toavoid a radical mechanism for polymerization of the phosphazenederivatives.

In one aspect, the invention provides polymerizable phosphazenederivatives with the following structural formula

    [--NP(A).sub.a (B).sub.b --].sub.x

wherein the groups A and B are bonded to phosphorus atoms through --O--,--S--, --NH--,or --NR-- (R=C₁ -C₆ alkyl); A contains at least one vinylether group of the general formula Q--O--CR'═CHR" and/or styrene ethergroup of the general formula ##STR1## wherein R' and/or R" stands forhydrogen or C₁ -C₁₀ alkyl; B stands for a reactive or nonreactivehydrocarbon group optionally containing O, S, and/or N, and optionallycontaining at least one reactive group; Q is an aliphatic,cycloaliphatic, aromatic, and/or heterocyclic hydrocarbon group,optionally containing O, S, and/or N; a is a number greater than O; b is0 or a number greater than 0 and a+b=2; x stands for a whole number thatis at least 2; and z stands for 0 or 1.

The open bonds in the formulae above indicate either joining into a ringwith alternating atoms of N and P, or a bonding to groups A or B or theusual catalyst or initiator molecule groups. The later, for example, canbe found in Makromol. Chem., 183; 1833-1841 (1982) and Makromol. Chem.,183; 1843-1854 (1982) or can be those of Lewis acids, SbCl₃, AlCl₃, orsulfur compounds.

The phosphazene derivatives of the invention can contain two or moredifferent vinyl ether groups and/or both vinyl ether groups and styreneether groups in one molecule. The phosphazene derivatives of theinvention, which can be polymerized cationically at least whensubstituted by vinyl ether groups, and whose polymerization can beinitiated by acids, have one or more of the following advantages overknown phosphazene derivatives: complete substitution of the phosphazeneand thus absence of chlorine can be achieved in high yields; oxygen doesnot inhibit the curing of the phosphazene derivatives of the invention;even thin coatings are completely cured in the presence of atmosphericoxygen, which makes thermally initiated curing possible in particular;they have no tendency to discolor the polymerized product; they areordinarily less viscous and therefore more suitable for low-solventapplication; and they have less tendency to shrink.

All of these properties make the polymerizable phosphazene derivativesof the invention suitable as curable binders for paints, coatings,fillers, mastics, adhesives, moldings, or films, especially as bindersfor paints and coatings. For example, they can be used advantageously asbinders in transparent coatings for exterior varnishing, or forvarnishing interior wood trim in motor vehicles. They can also be usedin transparent coatings for polycarbonate headlight diffusion lenses orthe like. The usual additive substances such as initiators, pigments,leveling agents, pigments, UV stabilizers, fillers, and the like, can beadded to formulations containing the polymerizable phosphazenederivatives of the invention.

The structural formula for the phosphazene derivatives of the invention,shown above, states that they are necessarily at least partiallysubstituted on the phosphorus atoms by groups that contain at least onevinyl ether group and/or styrene ether group, as shown and described.Therefore, the substituent B may be, but does not have to be, present inthe phosphazene molecule (i.e., b may be 0).

The phosphazene derivatives of the invention can be cyclic or acycliccompounds, which have a structural skeleton of alternating nitrogen andphosphorus atoms in every case. The cyclic compounds in which x standsfor 3 or 4 and which, therefore, consist of 6- or 8-membered rings arepreferred. The 6-membered ring, in which x stands for 3, is particularlypreferred.

Q is a spacer group that is bonded to a phosphorus atom through anoxygen atom, a sulfur atom, an NH group, or an NR group, and that has atleast one vinyl ether group and/or styrene ether group, in which R' andR" have the meanings given above, at its free end and/or as a sidegroup. R' and/or R" in these groups are preferably hydrogen, methyl, orethyl, and preferably are hydrogen.

Compounds especially preferred according to the invention are those withthe general structural formula ##STR2## wherein Z and Z' are the same ordifferent and each stands for --O--, --S--, --NH, or --NR-- (R=C₁ -C₆alkyl); Q stands for an aliphatic, cycloaliphatic, aromatic, and/orheterocyclic hydrocarbon group optionally containing O, S, and/or N; YHstands for an aliphatic, cycloaliphatic, aromatic, and/or heterocyclichydrocarbon group optionally containing O, S, and/or N and/or optionallycontaining a reactive group different from a vinyl ether group or astyrene ether group; y is O or 1; x stands for a whole number from 2 to20; and a, b, R', and R" are as defined above.

R in the above formulas is alkyl with 1 to 6 carbon atoms, preferablymethyl or ethyl. In the last formula given above, Z and Z' arepreferably --O--.

The spacer group Q and the YH group can have such structures that theycontrol the properties of the phosphazene derivative. Thus, the Q and YHgroups can have very diverse structures. Examples of such Q and Y groupscan be found in German patent document DE-A-4 325 776. They are usuallyalkaline groups with various chain lengths, straightchained or branched,preferably with 2 to 20 carbon atoms, and especially with 2 to 6 carbonatoms, biphenylene, phenylene or oxyalkylene groups, or combinationsthereof. In the case of oxyalkylene groups, they are preferablyoxyalkylene groups with the formula --(CH₂ -CH₂ -0)_(n), wherein n is 1to 20, preferably 1 to 6. The spacer groups Q and Y can optionallycontain substituents on this preferred structural formula, or can beinterrupted by other groups. Examples of such substituents are estergroups, keto groups, OH groups, or NH₂ groups. Examples of groupsinserted into the alkaline chain in turn are ester groups, keto groups,urethane groups, or NH groups.

The YH group can be straight-chained or branched, and can consist of areactive or nonreactive group or can contain a group that differs fromthe vinyl ether and styrene ether groups of the above formulas.Preferred reactive YH groups are or contain isocyanate groups, carboxylgroups, allyl groups, vinyl acetate groups, N-methylol groups, epoxidegroups, glycidyl ether groups, acrylate groups, methacrylate groups,silyl groups (such as C₁ -C₆ alkoxysilyl or aceeoxysilyl groups), OHgroups, or NH₂ groups. The reactive groups can also be blocked in theusual way. The selection of the YH group, however, is not to be limitedto the above enumerated groups.

The preferred phosphazene derivatives of the invention are those inwhich y is O or 1, i.e., those that are vinyl ether derivatives. In anycase, they can be cured with cationic initiation using at least oneacid. This can be done by direct addition of acid. Instead of this,initiators can be added to the formulation that split off acids whenirradiated with UV light or electron beams or when the temperature israised, which in turn then initiate the polymerization. If the moleculecontains other reactive groups in addition to the vinyl ether groups,multicure procedures can be used, for example, combinations of thermalcuring, curing by atmospheric humidity or atmospheric oxygen, and UVcuring.

The phosphazene derivatives containing styrene ether groups of theinvention are ordinarily polymerized in the usual way by a radicalmechanism. Thus, optionally, either initiators that split off radicalswhen irradiated with UV light or in some other way are added, orradicals are generated without addition of initiator by, for example,introducing thermal energy or by electron irradiation. Anionic orcationic polymerization is also possible in certain cases.

The phosphazene derivatives pursuant to the invention can be prepared byreacting a chlorophosphazene with at least one compound of the generalformula MA, alone or in combination with at least one compound of thegeneral formula MB, or successively with MA and MB, in an inert solvent.In these compounds, A and B are as defined above and M stands for ahydrogen atom, an alkali metal, an alkaline earth metal, or a basicgroup. The basic group M, for example, can be a pyridyl group or atertiary amino group such as a triethylamino group, or it can be a1,8-diazabicyclo[5,4,0]undec-7-ene(1,5-5) group. It is preferred for Mto be sodium. The compounds MA and MB can be obtained by reacting thecompounds HA and/or HB with sodium hydride, sodium metal, or sodiumhydroxide, for example, by the procedure of U.S. Pat. No. 4,775,732(US-A-1 4 775 732).

In accordance with the above embodiments, the preferred compounds MA arethose with the formula ##STR3## and the compounds MB are those with thegeneral formula M--Z'--YH, wherein M, Z, Z', Q, Y, R', R", and y are asdefined above.

The preferred process for preparing the phosphazene derivatives of theinvention consists of using compounds MA and MB in which M is bonded toan oxygen atom, and thus Z and Z' stand for --O-- in the above preferredformulas for MA and MB. Examples of practical inert solvents in whichthe reaction is carried out are tetrahydrofuran, toluene, dimethylsulfoxide, dimethylformamide, chloroform, methylene chloride, andpyridine. Suitable reaction temperatures are between 15 and 110° C.,preferably between 18 and 70° C., with lower temperatures requiringlonger reaction times. Depending on the temperature selected, it isdesirable for the reaction times to be between 5 and 60 hours.

DETAILED DESCRIPTION OF THE INVENTION

The invention is described in detail by the following examples.

EXAMPLE 1

The compound2,2,4,4,6,6-Hexakis(vinyloxyethylenoxy)-2,2,4,4,6,6-hexahydro-1,3,5,2,4,6-triazatriphosphorineis prepared by the following reaction. ##STR4##

16.80 g (0.10 mole) of sodium hydride (95%) is suspended in 700 ml ofanhydrous THF and/or argon in a 2-liter three-necked flask with internalthermometer, dropping funnel, and reflux condenser.

While cooling in an ice bath, 61.67 g (0.70 mole) of ethylene glycolmonovinyl ether is then added slowly through a dropping funnel over aperiod of 90 min. The internal temperature rises slightly, but remainsbelow 20° C. Stirring is then continued at room temperature for a totalof 48 h (alternatively 20 h at about 50° C.). The contents of the flaskgradually assume a brown color.

A solution of 34.79 g (0.10) mole of phosphonitrile chloride (NPCl₂)₃ in200 ml of anhydrous THF is then added slowly (90 min) through a droppingfunnel. Water bath cooling is necessary during this addition to keep thetemperature below 30° C. Stirring is continued for 1 h longer at roomtemperature, and the batch is then heated to an internal temperature of50° C. Stirring is continued overnight (total 24 h) at this temperature.

The mixture is then allowed to cool to room temperature and is filteredby suction. Almost all of the THF is removed from the brown filtrate ina rotary evaporator, 250 ml of diethyl ether and 250 ml of deionizedwater are added, and the mixture is transferred to a separatory funnel.The ether phase is separated, and the aqueous phase is extracted twomore times with 125 ml portions of diethyl ether. The combined etherphases are shaken three times with 50 ml portions of deionized water,which can lighten the mixture considerably. The ether phase is separatedand dried over sodium sulfate. After filtering off the drying agent andevaporating the solvent in a rotary evaporator, 62.84 g (0.096 mole,corresponding to 96% of the theoretical amount) of a clear yellow liquidis obtained.

For further purification, the crude product can be stirred with diethylether and activated charcoal, filtered through a short silica gel column(Silica Gel 60, mobile phase diethyl ether), and then evaporated. Theproduct is then pure in TLC and HPLC. Yield after purification: 60.23 g(0.092 mole, corresponding to 92% of the theoretical amount). Thepurified product crystallizes after trituration with a glass rod(crystal nucleation).

The phosphonitrile chloride was recrystallized from n-heptane. The vinylether was not further purified. The tetrahydrofuran was stored overDeperox molecular sieve and is anhydrous. The other chemicals are usedwithout additional purification.

Properties of the product:

White, sticky solid; melting point 26-27° C., gradual browndiscoloration (without polymerization) above 230° C.; index ofrefraction (of the noncrystallized liquid) n_(d) ²⁵ =1.4914.

    ______________________________________                                        Elemental analysis:                                                                       N %     P %    O %   H %  Cl % O %                                ______________________________________                                        Calculated: 6.39    14.13  43.84 6.44 0.00 29.20                              Found:      6.20    14.29  44.07 6.54 0.00                                    ______________________________________                                    

Molecular weight 657.53; readily soluble in chloroform, tetrahydrofuran,diethyl ether, isopropanol, ethyl acetate, toluene, poor solubility inn-heptane, n-pentane; thin layer chromatographic test, developern-heptane/ethyl acetate 1:1, material silica gel with UV indicator RothCo., Rf=0.40; detection TV 254 nm; indicator Methyl Red, iodine;Beilstein test for halogens negative.

EXAMPLE 2

2,2,4,4,6,6-Hexakis(vinyloxyhexyloxy)-2,2,4,4,6,6-hexahydro-1,3,5,2,4,6-triazatriphosphorine:

The compound named above is prepared by the process described in Example1, from 14.42 g (0.10 mole) 1,6-hexanediol divinyl ether, 2.40 g (0.10mole) sodium hydride, and 4.29 g (0.012 mole) (NPCl₂)₃.

Properties:

Clear, viscous, slightly yellow-colored liquid; yield 10.64 g (0.011mole, corresponding to 89% of the theoretical amount); molecular weight993.57 g/mole; index of refraction n_(d) ²⁵ =1.4804; Beilstein test forhalogens negative; thin layer chromatographic test: mobile phase ethylacetate, material silica gel with UV indicator Roth Co., Rf=0.27;detection UV 254 nm, indicator Methyl Red, iodine.

EXAMPLE 3

2,2,4,4,6,6-Hexakis (vinyloxybutyloxy)-2,2,4,4,6,6-hecxahydro-1,3,5,2,4,6-triazatripnosphorine:

This compound is prepared by the method described in Example 1 from11.62 g (0.10 mole) 1,4-butanediol divinyl ether, 2.40 g (0.10 mole)sodium hydride, and 4.97 g (0.014 mole) (NPCl₂)₃.

Properties:

Clear, viscous, pale yellow-colored liquid; yield 7.60 g (0.009 molecorresponding to 67% of the theoretical amount), molecular weight 825.39g/mole; index of refraction n_(d) ²⁵ =1.4814; Beilstein test forhalogens negative; thin layer chromatographic test: mobile phasen-haptene/ethyl acetate 1:1; material silica gel with UV indicator RothCo., Rf=0.55, detector UV 254 nm, indicator Methyl Red, iodine.

EXAMPLE 4

2,2,4,4,6,6-Hexakis[vinyloxydl(ethylenoxy)]-2,2,4,4,6,6-hexahydro-1,3,5,2,4,6-triaztriphosphorine:

This compound is prepared by the method described in Example 1, with asomewhat longer reaction time, from 13.27 g (0.10 mole) diethyleneglycol; monovinyl ether, 2.40 g (0.10 mole) sodium hydride, and 4.97 g(0.014 mole) (NPCl₂)₃.

Properties:

Clear, viscous, slightly yellow-colored liquid; yield 9.68 g (0.011mole, corresponding to 75% of the theoretical amount), molecular weight921.36 g/mole; Beilstein test for halogens negative; thin layerchromatographic test: mobile phase ethyl acetate; material silica gelwith UV indicator Roth Co., Rf=0.70, detector UV 254 nm, indicatorMethyl Red, iodine; readily soluble in dichloromethane, chloroform,tetrahydrofuran; poor solubility in water, n-haptene.

EXAMPLE 5

The compound2,2,4,4,6,6-Hexakis(3'-vinyloxypropylamino)-2,2,4,4,6,6-hexahydro-1,3,5,2,4,6-triazatriphosphorineis prepared by the following reaction: ##STR5##

20.23 g (0.20 mole) of 3-amino-1-propanol vinyl ether is placed in a259-ml three-necked flask with dropping funnel, reflux condenser, andinternal thermometer, and 50 ml of anhydrous toluene is added. Asolution of 4.97 g (0.014 mole) of (NPCl₂)₃ in 50 ml of toluene is thenadded over a period of 20 min while cooling with a water bath. Theinternal temperature rises slightly. After the addition is about halfcomplete, a white precipitate of hydrochloride is formed. Stirring iscontinued for 150 min at room temperature, and the mixture is thenheated to an internal temperature of 50° C. The mixture is stirred atthis temperature for 18 h, and is then allowed to cool to roomtemperature. The mixture is filtered by suction, and the filtrate isshaken with 15 ml of deionized water, dried over anhydrous sodiumsulfate, and filtered. The solvent is then drawn off from the organicphase obtained in a rotary evaporator. After brief drying under highvacuum, 12.21 g of an orange, highly viscous, clear liquid is obtained.

The product is taken up in toluene and filtered through a short silicagel column (Silica Gel 60); yield after removal of solvent and dryingunder high vacuum 9.70 g (0.013 mole, corresponding to 94% of thetheoretical amount) of clear, yellow, highly viscous liquid.

Properties:

Molecular weight 735.78 g/mole; thin layer chromatographic test: mobilephase ethyl acetate, material silica gel, with UV indicator Roth Co.,Rf=0.80; detection: indicator MethYl Red, iodine.

EXAMPLE 6

Vinyl ether phosphazene derivative with mixed substitution are preparedaccording to the following reaction: ##STR6##

a) 9.60 g (0.40 mole) of sodium hydride is placed in a 1000-mlthree-necked flask with KPG stirrer, dropping funnel, and internalthermometer, and is slurred with 100 ml of anhydrous tetrahydrofuran.While cooling with ice/salt, a solution of 65.68 g (0.40 mole) ofeugenol in 50 ml of anhydrous tetrahydrofuran is then added dropwise(gas evolution, addition time 45 min).

Stirring is continued for 1 h at room temperature, and then a solutionof 46.36 g (0.133 mole) of (NPCl₂)₃ in 150 ml of anhydroustetrahydrofuran is added, likewise while cooling with ice/salt (additiontime 15 min, gelatinous precipitation of NaCl, flask contentsgray-green).

The mixture is stirred for 60 h at room temperature, transferred to asingle-necked flask, and the solvent is evaporated by rotation. Theproduct is taken up in 150 ml of diethyl ether and 150 ml of deionizedwater, and the phases are separated in a separatory funnel. The aqueousphase is washed twice with 10 ml portions of deionized water. Thecombined orange-colored ether phases are dried over anhydrous sodiumsulfate. The drying agent is filtered off and the clear filtrate isstirred for 30 min at room temperature with activated charcoal. Afterrepeated filtration and solvent removal by rotary evaporation, 94.94 g(0.130 mole, corresponding to 98% of the theoretical amount) of aviscous, clear, brown-colored liquid is obtained.

For purification, the product is filtered through a short silica gelcolumn (Silica Gel 60) mobile phase n-heptane/ethyl acetate 1.1). Thesolvent is removed by rotary evaporation and the product is dried on anoil pump. Yield 87.62 g (0.120 mole, corresponding to 90% of thetheoretical amount) of highly viscous, light yellow clear liquid.

Properties of the intermediate:

Molecular weight 730.89 g/mole; Beilstein test for halogen-positive;index of refraction n_(d) ²⁰ -1.5723; readily soluble in toluene,chloroform, ethyl acetate, diethyl ether, tetrahydrofuran, acetone; poorsolubility in water, n-heptane; the product consists of isomericcompounds.

    ______________________________________                                        Elemental analysis:                                                                       C %     H %    N %   O %  Cl % P %                                ______________________________________                                        Calculated: 49.38   4.56   5.76  13.10                                                                              13.39                                                                              12.76                              Found:      49.63   4.66   5.61       14.61                                                                              12.81                              ______________________________________                                    

Thin layer chromatographic test: developer ethyl acetate; materialsilica gel with UV indicator Roth Co., Rf=0.71; detection UV 254 nm,indicator Methyl Red, iodine.

b) 4.46 g (0.144 mole) of sodium hydride is placed in a 250-mlthree-necked flask with dropping funnel, reflux condenser, and internalthermometer, and is slurried with 100 ml of anhydrous tetralydrofuran.The mixture is stirred for 5 min, and a solution of 12.69 g (0.144 mole)of ethylene glycol monovinyl ether in 20 ml of anhydrous tetrahydrofuranis then added over a period of 30 min while cooling with a water bath.The mixture is then heated to an internal temperature of 50° C. andstirred for 40 hours. The flask contents are then cooled down to roomtemperature.

While cooling with a water bath, a solution of 30.00 g (0.041 mole) of(NP[O--C₆ H₃ {OCH₃ }C₃ H₅ ]Cl)₃ in -70 ml of anhydrous tetrahydrofuranis then added dropwise over a period of 1 hour. The mixture is stirredfor 3 h at room temperature and is then heated to an internaltemperature of 50° C. After stirring for 40 h at the temperature thebrown contents of the flask are allowed to cool to room temperature,transferred to a single-necked flask, and the solvent is evaporated byrotation. The product is taken up in 130 ml deionized water and 130 mlof chloroform, and the phases are separated in a separatory funnel. Theaqueous phase is again shaken with 50 ml of chloroform. The combinedorganic phases in turn are washed twice with 50 ml portions of 5% sodiumchloride solution, and then dried over anhydrous sodium sulfate. Afterfiltering off the drying agent, removing the solvent by rotary drying,and drying under high vacuum, 35.83 g (0.040 mole, corresponding to 99%of the theoretical amount) of a pasty, caramel-colored compound isobtained.

For purification, the product is stirred with activated charcoal andfiltered through a short silica gel column (Silica Gel 60). Afterdrawing the solvent off from the filtrate and drying the product underhigh vacuum, 28.37 g (0.032 mole, corresponding to 78% of thetheoretical amount) of pale-colored pasty product is obtained.

Properties of the end product:

Molecular weight 885.2 g/mole; Beilstein test for halogen negative; thinlayer chromatographic test: mobile phase n-heptane/ethyl acetate 1:1;material silica gel with UV indicator Roth Co., Rf=0.47; detection UV254 nm, indicator Methyl Red, iodine.

    ______________________________________                                        Elemental analysis:                                                                       C %     H %    N %   O %  Cl % P %                                ______________________________________                                        Calculated: 56.95   6.14   4.74  21.67                                                                              0.00 10.19                              Found:      57.41   6.33   4.68       0.00 11.00                              ______________________________________                                    

EXAMPLE 7

The compound2,2,4,4,6,6-Hexakis(styrenoxy)-2,2,4,4,6,6-hexahydro-1,3,5,2,4,6-triazatriphosphorineis prepared according to the following reaction: ##STR7##

a) 38.88 g (0.24 mole) of p-acetoxystyrene is placed in a 500-mlthree-necked flask with internal thermometer, and 400 ml of a 10%potassium hydroxide solution is added over a period of 2 min whilestirring and cooling in a water bath. The flask contents turn yellow,two phases form, and the internal temperature rises slightly. Themixture is first stirred for 2 h longer while cooling in a water bath,and is then stirred overnight at room temperature (about 15 h).

On the next day, the contents of the flask are orange-colored andconsist of one phase only. It is neutralized with about 175 ml of 3 Nhydrochloric acid (pH control). The voluminous product precipitates out.It is filtered off by suction and washed with some n-heptane. The crudeproduct is dried under oil pump vacuum to determine the crude yield.

Crude yield 24.84 g (0.207 mole, corresponding to 86% of the theoreticalamount) of light pink powder. It is dissolved in 200 ml of chloroformand shaken twice with 50 ml portions of deionized water. The organicphase is dried over anhydrous sodium sulfate and, after filtering offthe drying agent, it is stirred for 10 min with activated charcoal. Itis filtered repeatedly and the solvent is drawn off in a rotaryevaporator.

Crude yield was 18.11 g (0.151 mole, corresponding to 63% of thetheoretical amount) of white powder. For further purification, it isrecrystallized from a mixture of 100 ml of chloroform and 50 ml ofn-heptane (white crystals form quickly on standing in a refrigerator).Yield after suction filtration and drying was 12 84 g (0.107 mole,corresponding to 54% of the theoretical amount) of white powder. Theprepared p-hydroxystyrene should be used immediately since it can becomediscolored on lengthy storage.

Properties of p-hydroxystyrene:

White solid; melting point 68 to 70° C.; molecular weight 120.15 g/mole,readily soluble in acetone, tetrahydrofuran, ethanol, diethyl ether,poorly soluble in n-heptane, water; thin layer chromatographic test:developer n-heptane/ethyl acetate 1:1; material silica gel with UVindicator Roth Co., Rf=0.50; detection UV 254 nm, indicator Methyl Red,iodine.

    ______________________________________                                        Elemental analysis:                                                                         C %         H %    O %                                          ______________________________________                                        Calculated:   79.97       6.71   13.32                                        Found:        79.73       6.66                                                ______________________________________                                    

b) 2.08 g (0.087 mole) of NaH is suspended in 130 ml of anhydroustetrahydrofuran in a 500 ml three-necked flask and the mixture isstirred for 5 min at room temperature. A solution of 12.84 g ofp-hydroxystyrene and 0.01 g of sulfur (inhibitor) in 100 ml of anhydroustetrahydrofuran is then added dropwise over a period of 30 min (gasevolution, rise of internal temperature to 30° C.; the contents of theflask quickly become brown-colored).

The mixture is stirred for 30 min longer at room temperature, and thealkoxide formation is then complete (no further evolution of gas, clearbrown solution). A solution of 3.77 g (0.011 mole) of (NPCl₂)₃(recrystallized from n-heptane) in 40 ml of anhydrous tetrehydrofuran isthen added dropwise over a period of 15 min (slight internal temperaturerise). After the addition is complete, stirring is continued for 1 hlonger at room temperature, and the mixture is then heated to aninternal temperature of 60° C. (immediate precipitation of NaCl).Stirring is continued overnight at this temperature (15 h in all).

The mixture is allowed to cool to room temperature and the contents ofthe flask are transferred with a little tetrahydrofuran into a 1-literround-bottomed flask. Most of the solvent is evaporated by rotation, andthe crude product is transferred into a separatory funnel by means of100 ml or diethyl ether and 100 ml of deionized water. The phases areseparated, and the brown aqueous phase is extracted twice with 50 mlportions of diethyl ether. The combined ether phases (yellow-orange) areshaken in succession with 30 ml each of 2 N hydrochloric acid, 5% sodiumcarbonate solution, and 5% sodium chloride solution, and are then driedover anhydrous sodium sulfate. The mixture is filtered, the filtrate isstirred for 10 minutes with activated charcoal, filtered again, and theether is evaporated by rotary evaporation. Crude yield was 11.90 g(0.014 mole, corresponding to >100% of the theoretical amount) of whitepowder.

For further purification, the product is recrystallized from 50 ml, ofisopropanol. Final yield was 7.90 g (0.009 mole, corresponding to 85% ofthe theoretical amount) of white powder.

Properties:

White solid; melting point 99 to 100° C.; thermal behavior: gradualpolymerization above 120° C.: molecular weight 849.89 g/mole; readilysoluble in tetrahydrofuran, dichlcromethane, diethyl ether, toluene,acetone; poorly soluble in water, n-heptane; thin layer chromatographictest: developed system n-heptane/ethyl acetate 1:1; material silica gelwith UV indicator Roth Co., Rf=0.03; detection UV 254 nm, indicatorMethyl Red, iodine; Beilstein test for halogens negative.

    ______________________________________                                        Elemental analysis:                                                                       C %     H %    N %   O %  Cl % P %                                ______________________________________                                        Calculated: 67.84   4.98   4.94  11.30                                                                              0.00 10.93                              Found:      67.88   5.12   4.82       0.00 10.76                              ______________________________________                                    

What is claimed is:
 1. A method of using a polymerizable phosphazenederivative comprising adding the phosphazene derivative to a compositionas a curable binder for paints, coatings, fillers, mastics, adhesives,moldings, or films, wherein the phosphazene derivative is of the generalformula

    [--NP(A).sub.a (B).sub.b --].sub.x

wherein the groups A and B are bonded to phosphorous atoms through--O--, --S--, --NH--, or --NR--, wherein R is a C₁ --C₆ alkyl group, Acontains at least one of a vinyl ether group of the general formulaQ--O--CR'=CHR" and a styrene ether group of the general formula ##STR8##wherein at least one of R' and R" are hydrogen or a C₁ -C₁₀ alkyl group;B is a reactive or nonreactive hydrocarbon group optionally containingat least one of O, S, and N, and optionally containing at least onereactive group; Q is one of an aliphatic, cycloaliphatic, aromatic, andheterocyclic hydrocarbon group optionally containing at least one of O,S, and N; a is a number greater than 0, b is 0 or a number greater than0; a+b=2, x stands for a whole number that is at least 2; and z standsfor 0 or
 1. 2. A method of using a polymerizable phosphazene derivativeaccording to claim 1, wherein ##STR9## and B=Z'--YH so that thephosphazene derivative is of the general formula ##STR10## wherein Z andZ' are the same or different and each stands for --O--, --S--, --NH--,or --NR-- wherein R is a C₁ -C₆ alkyl; Q is at least one of analiphatic, cycloaliphatic, aromatic, and heterocyclic hydrocarbon groupoptionally containing at least one of O, S, and N; YH stands for atleast one of an aliphatic, cycloaliphatic, aromatic, and heterocyclichydrocarbon group optionally containing at least one of O, S, and N andoptionally containing a reactive group different from a vinyl ethergroup or a styrene ether group;y is 0 or 1; x is a whole number from 2to 20; and a, b, R' and R" are defined as in claim
 1. 3. A methodaccording to claim 1, further comprising cationic initiation curing saidphosphazene derivative with at least one acid, wherein said phosphazenederivative comprises a vinyl ether group.
 4. A method according to claim3, wherein Z and Z' are oxygen.